Azo dye



Patented Dec. 11, 1928.

UNITED sTA'rEs PATENT OFFICE.

HERMANN WAGNER, OF HOCHST-ON-THE-MAIN, GERMANY, ASSIGNOB, BY MESNE ASSIGNMENTS; TO GRASSELLI DYESTUFF CORPORATION, OF NEW YORK, N. .Y., A

CORPORATION OF DELAWARE.

AZO DYE.

N0 Drawing. Application filed February 12, 1923, Seriai No. 618,710, and in Germany February 24, 1922.

In further developing the inventive idea set forth in U. S. Patent 1, 193,577,'according to Which by combining certain halogensubstituted diazo compounds with a halogen substituted toluidide of 2.3-hydroxynaphthoic acid dyestuffs are obtained of particularly great tastness, above all of a particularly striking fastness to kier-boiling and to light, I have found that dyestuffs of equally excellent fastness, particularly a striking fastness to kier-boiling, are produced by the combination of any diazo compound with an a'rylamide of the 2.3-l1ydroxynaphthoic acid. halogenated in the aryl residue and substituted by an alkylor alkyloxygroup in the para position of the imino group. I have furthermore found that azo dyes of equally good fastness are obtained by coupling halogenated diazo components containing an alkylor alkyloXy-group with arylamides of the 2.3'hydroxynaphthoic acid not halogenated in the aryl residue but containing in the para position. to the imino group an alkylor alkyloxfly group. The preparation of the dyestuffs may be effected in solution which gives pigment-dyestuffs; the coupling may however, also be carried out on the fibre in printing as Well as in pieceand yarn dyeing.

E examples.

1 PN. It is then dried and printed With the printing colour obtained by mixing 15.2 gr. of oanisidine with 2 1 com. of hydrochloric acid 22 Be. to a paste in the presence of 200 com. of Water, cooling with 150 gr. 0t ice, adding a solution of 8 gr. of sodium nitrite in com. of Water and thereafter 550 er. of tragacanth 6011000, to Which reaction mixture there is added,' before use 20 gr. of sodium acetate.

The structural formula of the dyestuif is as follows:

Para-soap PN designates ammonium ricinoleate. By the term tragacanth 1000 is meant a solution of 60 parts by Weight of tragacanth in 1000 parts of Water.

2. Yarn printed with the aqueous preparation which contains. in one liter: 12 .7

of 2.3hydroxynaphthoic acid-chloroanisidide (NIIIGlZOCPL lIiiId). 20 com. of 3 Be. caustic soda solution, and 30 cons. of sodium Turkey red oil 50%. The so-impregnatod yarn is wrung out and dyed With the diazo-solution which is obtained by dissolving 14.1 gr. of 4-chloro-2-toluidine in 24 com. of hydrochloric acid 22 B. and 200 com. of boiling Water, cooling with 150 gr. oi ice treating With a solution of 8 gr. of sodium nitrite in 50 com. of water While stirring, making up to 4 liters with Water, and adding, before use, 20 gr. of sodium acetate.

After dyeing, the yarn is Well wrung out, Washed, and soaped.

The dyestu'fi? has most probably the lowing structural formula:

fol-

3. Material is padded With an aqueous solution containmg, in one liter: 20 gr. of

2.3-hydroxynaphthoic acid-chloro-anisidide (NH:CIIOCH =1:3:4), 60 gr. of 22 Be. caustic soda solution and 20 gr. of para-soap PN. It is then dried and printed with the printing color obtained by mixing 15.? of chloro-anisidine (OCH NH Cl 1 12:4) with 200 com. of water and 2 coin. of hydrochloric acid 22 Be. to a paste, cooling; with 150' gr. of ice, adding asolutiou of 8 gr. of sodium nitrite in 50 com. of water, adding ,550 gr, of tragacanth 60:1000, and, before use, further adding 20 gr. of sodium acetate.

The'dyestuff has most probably the following structural formula:

OCHs

printed with the printing color obtained as follows: 16.8 gr. of l-chloro-S-anisidi'ne are dissolved in 24: com. of hydrochloric acid 22 B. and 200 com. of boiling water; the result- .ing solution is then w ll cooled by the addition of 150 gr. of ice; there is then added, while stirring, a solution of 8 of sodium nitrite .in 50' com. of water, and the whole is made up to 500 gr. with water. This diazosolution is thickened with 480 gr. of tragacanth 1000. Before use, there are added v 20 gr. of sodium acetate cryst.

The dyestufi' has most probably the follow- I ing structural formula:

' caustic soda solution and 20gr.'of para-soap PN. It is: thenwdried and printed with a printing'color which is prepared as follows: 17 .5 gr. of 4-chloro-2-toluidine are dissolved a solution. Before use, there are added further 20 gr. of sodium acetate.

The dyestuff has mostprobably the following structural formula:

6. Material is padded with an aqueous solution containing, in one liter: 27 gr. ofi2.8- hydroxynaphthoic acid-chloro-phenetidide (NH: Cl :'O.C H =l:2: l), 60 gr. of22 B caustic sodasolution, and 20 gix of para-soap PN. It is then dried, and printed "w a printing color which is prepared as follows: 15.? gr. of para-chloro anisidi1ie is mixed. to a paste with 200 com. of water and 2e i-ccrn.

of hydrochloric acid. 22 B.. 150 gr. ice

are added, and thereafter a solution of 8 of sodium nitrite in 50 com, of water. The resulting,diazosolution is thickened by the addition of 550 gr. of tragacanth 6011000. Before use, 20 of sodium acetate are added.

The dycstuff has most probably the following structural formula:

is added, to make up to 500 gr. This diazosolution is thickened with 480 gr. of tragacanth (3'0 1000. Before use, there are added 20 9:12 of sodium acetate cryst.

The dyestuii' has most probably the following structural formula:

8. Material is padded with an aqueous solution containing,'in one liter: 23.7 gr. of 2.3-hydroxynaphthoic acid-o-chlorol-toluidide (NH:CH Cl=1:4:5), 80 com. of 22 B. caustic soda solution, and 20 of parasoap PN. It is then dried, and printed with the printing color prepared as follows: 1%,?) gr. of a-naphthylainine base are dissolved, with heating, in 200 com. of water and 10 ccm. of hydrochloric acid 22 Be. The solu tion is cooled, and thereafter there are {H 20 ecm. of hydrochloric acid 22 Be, and 150 of ice. After cooling to 6., there are poured into the solution, with stirring, 20 cr-m. of a. sodium nitrite solution containing; 290 er. of sodium nitrite per liter. The waole is filtered, made up to 500 with water, and added to 170 grj of tragacanth 60 1000, with stirring. Before use, there are added further 30 gr. of sodium acetate.

1 Ha ti 10. Yarn is impregnated with an aqueous preparation containing, inone liter: 11.8 V of 2.8-hydroxynaphthoic acid--chlorotoluidide (NI-I: CH Cl=1z 4: 5) ccm. of 345 Be. caustic soda solution and 80 ccm. of sodium Turkey red oil 50%. The impregi'lat-ed yarn is wrung out, and dyed with a diam-solution prepared as follows: 2.8 of 2.2 dichloro-benzidine are made into a paste with com. of hydrochloric acid 20 B. and 20 ccm. of water; gr. of ice are added,

The dyestufi has the following structural formula: 7

9. Material i'spadded with an aqueous preparation containing, in one liter 35.9 gr. of 2.3-hydroxynaphthoic acid-E-chlorod-anisidide (NH :OCH :01 1 A) 115 00111. of 22 B. caustic soda solution, and 25 gr. of parasoap PN. It is then dried, and printed with a printing color obtained as IOllGWS: 145i gr. of henzidine base are dissolved in 150 com. of boiling water and 16 com. of hydrochloric acid 22 B.; the solution is cooled by the ad- '-d.ition of 200 of ice, and 27.2 ccm. of hyand thereafter 1.5 gr. of a solution of sodium nitrite (containing 290 gr. of sodium nitrite per liter) are added while'stirring; the whole is made up with cold water to 1 liter. Before use, there are added thereto 1 gr. of sodium acetate.

After dyeing, the yarn is well Wished, and soaped. 2

The dyestuff has most probably the following structural formula:

11. Into an aqueous suspension containing, in one liter: 6.54 gr. of sodium salt of 2.3- hydroxynaphthoic acid-5-chloro-4r-anisidide (Nl-1:O.CH Cl=1:4l:5),21 ccm. of22 B. caustic soda solution, and 1&6 gr. of spar, there is poured slowly, while stirring, the diazo-solution which is obtained as follows:

2.53 gr. of 3.3-dichloro-benzidine are dissolved in 200 com, of hot water and 1.6 ccm..

cooled by the addition of 600 ccm. of water and 100 gr. of ice, and to it are added 3.2 ccinaof hydrochloric acid 22 B. Into the cool solution there are introduced, while stirring 52 00111. of sodium nitrite solution (containing 290 gr. of sodium nitrite per liter). Before use, there are added A gr. of sodium acetate, and sufficient water to make 1 liter.

The dyestuff has mostprobably the followof hydrochloric acid 22 136.; the solution is ing structural formula:

'Having now described my invention,what I claim is: r

'1. As new products, the azo dyes of the general formula:

N:NR

Material dyed with the dyes of claim 1. Material dyed with the dyes of claim 2.

mooqmgn Ha1ogon ON- -X /\/g wherein X represents an alkylor alkylox group, and wherein R represents an aryl V residue which may be further substituted.

2. As new products, the azo dyes of the following formula:

wherein R represents an aryl residue which may be further substituted,

3. As new products, the azo dyes of the following formula:

wherein Y represents hydrogenior a chlorine atom, and Z represents hydrogen, alkyl. or alkyloxy, at least one Z being an alkyl or 'alkyloxy.

11. Material dyed with the dyes of claim 9. 12. Material dyed with the dyes of claim whereinR represents the residue of an aro-u rnatic compound of the benzene series which may be further substituted.

4:. As a new product, the azo dye of the following formula In testimony whereof,I affix my signature.

DR. HERMANN WAGNER.

. Material dyed with the dyes of claim 3. 

